Water-miscible glycidyl ethers



United States Patent WATER-MISCIBLE GLYCIDYLETHERS I Benjamin G. Wilkes,Jr., Wilkinsburg, and Arthur B. Steele, Pittsburgh, Pa., assignors toUnion Carbide and Carbon Corporation, a corporation of New York NoDrawing. Application December 20, 1951,

Serial No. 262,674

The present discovery relates to glycidyl'ethers. More particularly, itis concerned with new and improved glycidyl ethers which are misciblewith water in all proportions and capable of imparting a high degree ofwater- (Cahnmann et al. 2,501,026); These epoxide ethers arecharacterized by limited miscibility with water, bath monomer andpolymer. To structures capable of reacting therewith, they impart astrong organophilicproperty in contrast to the strong hydrophiliccharacteristics imparted by the glycidyl ethers of this invention.

The present improvement is based on our discovery that the glycidylethers of the monomethyl ethers of diethylene glycol, dipropylene glycoland ethylene propylene diglycol, HOCzH'4OC2Hs(CH3)OI-I, are misciblewith water in all proportions and capable of imparting a high degree ofwater miscibility to hydrophobic structures containing active Hydrogen,with resultant pro duction of surface active agents. In addition, theseglycidyl ethers which have eight, nine or ten carbon atoms to themolecule convert to polymers which are miscible with water in allproportions. The monomers can be represented by the following generalformula- C sO chasm owizuaaoonir npnl are listed in the followin table:

. Also, pressure equipment is not required for glycidyl ether PatentedApr. 24, 1956 As will be noted, these glycidyl ethers combine in thesame molecule the properties of water miscibility and high boilingtemperature. By the term high boiling temice perature, as used herein,is meant a boiling temperature at a reduced pressure of threemillimeters of mercuryabsolute of at least 80 C. with correspondinglyhigher boiling temperature at higher pressures. .By reason of the highboiling temperature and miscibility of the monomers and polymers withwater in all proportions taken together with their reactivity throughthe oxirane group,

present therein, these glycidyl ethers of the diglycol mono methylethers are useful and important as solubilizi'ng agents, aspolymerizable resin solvents, and as intermediates for chemicalsynthesis generally.

drogen atoms, for instance, alcohols, phenols, amines,

acids and the like. Thus, in reaction, with lauryl alcohol the glycidylether of diethylene glycol monomethyl other is approximately equivalentto ethylene oxide as a soluk bilizing agent but because of its'highboiling temperature, and-high flash point it can be used with few of thehazards attendant upon reactions where ethylene oxide is used.

conversions, or storage, as with ethyleneoxide. The

same is true also of the glycidyl ethers of 'dipropylene glycolmonomethyl ether and of ethylene propylene diglycol monomethyl ether.Our glycidyl ethers are also excellent solvents for nitrocelluloseandcan beused as polymerizable solvents in fluid epoxy resin systems.

Monomer Polymer diethylene glycol monomethyl eth r 6 4. 90-93 w m 5dipropylene glycolmonomethyl other 83-91 a: co 7 ethylene, propylenedlglycol,

monomethyl ether. 88-91 as m 6 1 Carbon factor Number of cal-b0 atomsper dxirane'group in the monomer, exclusive oi. the glycidylgroup orgroups.

Diglyoidyl ether of:

In contrast to the monoglycidyl ethers of the diglycol monomethyl ethersof the present invention are the monoglycidyl and diglycidyl ethers ofthe various glycols Whose properties are given in thefolloWing table.They are not a part of this invention.

TABLE II Boiling 'water lzggsebility at Temp. at Carbon 3 Factor MonomerPolymer Mouoglycidyl ether of:

ethylene glycoL. propanediol- 1,3 hutaiie'd'iol-IA. neutanetllolq,hexanediol-1,6 ethylene glycol mouomethylet-her. propylene glycolmonomethyl ether.

.. limited....

ethylene glycol propaned'iol lfi butanediol-L t entanediol-l,5exanediol-l,6.;..

' emperor-H an o 1 Carbon factor: Number or carbon atoms per o'xiranogroup an the monomer exclusive of the glycidyl groups.

With respect to the diglycidyl ethers of the 'gl'ycols,

it appears from the data of the foregoing table that the number ofcarbon atoms in the. glycolresidue is the critical factor in determiningwater miscibili'ty of the monomer, and that when the number of carbonatoms in the glycol residue (i. e., the molecule exclusive of theglycidyl group's) exceeds two per glycidyl group, the

monomer is not miscible with water. This observation seems to be borneout by a comparison of the waterm'iscibility of glycidyl ethers whichhave in the monomer residue (exclusive of the glycidyl group's.)morethan two carbon atoms per glycidyl grou 7 The oxirane group isreactive wtih compounds contaiuingactive hy-" 1 Carbon factor: Thenumber of carbon atoms in the monomer, exclusive of glycidyl groups, perglycidyl group.

In contrast to the foregoing, the monomers of the glycidyl ethers of thediglycol monomethyl ethers of this invention remain miscible with waterin all proportions when the number of carbon atoms in the molecule,exclusive of the glycidyl group, is as high as seven per glycidyl group,as in the case of the glycidyl, methyl diether of dipropylene glycol.

From Table II, it is to be noted that none of the lower aliphaticglycidyl ethers, excepting the glycidyl ethers of ethylene and propyleneglycol monomethyl cthers convert to polymers miscible with water in allproportions. These two diglycidyl ethers are not capable, however, ofimparting water-miscibility to hydrophobic'structures to the high degreewhich characterizes the compounds of this invention.

Concerning the relative efficiencies of these epoxides for convertingcommercial lauryl alcohol to water soluble derivatives possessingsurface-activity in water solution, the following weights of monomer arerequired to impart equivalent water solubility to 190 grams of thealcohol in the production of nonionic ether derivatives:

481 grams glycidyl ether of ethylene glycol monomethyl ether 415 gramsglycidyl ether of diethylene glycol monomethyl other 390 grams ethyleneoxide Draves wetting tests indicate that the surface-active agentderived from the glycidyl ether of diethylene glycol monomethyl ether issuperior in wetting power to that derived from the glycidyl ether ofethylene glycol monomethyl ether. The data appears in the followingtable:

TABLE IV Concentrations of solubilized lauryl alcohol in grams per 100milliliters of distilled water for various wetting times in Draveswetting tests Wetting Times Lauryl Alcohol Solubilized with--secseeseconds onds onds Glycidyl ether of ethylene glycol monomethylether Grams per 100 1111.. 0. 125 0. 077 O. 061 Glycidyl ether ofdiethylene glycol monomethyl ether .Grams per 100 11.11.. 0. 105 0. 0660. 047 Ethylene oxide do.-.. 0. 11 0. 065 0. 045

Our glycidyl others can be prepared by reacting epichlorhydrin with thediglycol monomethyl ether in the presence of a suitable catalyst, forinstance, boron trifluoride. The epichlorhydrin is preferably added tothe diglycol monomcthyl ether, dropwise. Upon completion of thereaction, the resulting alpha-glycerol chlorhydrin ether is then reactedwith an equivalent amount of alkali to dehydrochlorinate it. Theresultant glycidyl ether can then be recovered and purified, if need be.

The improvement is further illustrated ing examples.

by the follow- EXAMPLE 1 Glyeidyl ether of methoxyethoxyethanol CHzCHCHO C1350 C :H5O CH;

To 960 parts (8 mols) of diethylene glycol monomethyl ether containingas catalyst one milliliter of the ctherate of boron trifluoride wasadded dropwise 185 parts (2 mols) of epichlorhydrin. T he reactionmixture was maintained at a temperature of to C. After all theepichlorhydrin had been added and the exothermic reaction had subsided,the temperature was raised to 100 C. to insure complete reaction. Thereaction mixture was then distilled. After recovering the unreacteddiethylene glycol monomethyl ether, there was obtained 383 parts of thealpha-glyceryl chlorhydrin ether of diethylene glycol monomethyl ether.This amount represented a yield of per cent.

A mixture of 383 parts (1.8 mols) of the alpha-glycerol chlorhydrinether of diethylene glycol monomethyl ether with an equal amount ofdiethyl ether was cooled to 1 10 C. and 72 parts of sodium hydroxide inthe form of a 50 per cent aqueous concentrate was added at a uniformrate over a period of one hour. Thereafter the temperature was raised to100 C. over a period of two hours. By titration it was ascertained thatper cent of the sodium hydroxide had been used in thedehydrochlorination reaction. After the reaction mixture had beenfiltered to remove the salt, the other layer was separated and driedover sodium sulfate. Upon distillation, there was obtained 260 parts ofthe glyciclyl ether of diethylene glycol monomethyl ether representing ayield of 82 per cent. It was a colorless liquid which was miscible inall proportions with water.' It was characterized by the followingproperties: boiling temperature, 95--97 C. at 4 millimeters of mercury,pressure, abs; refractive index, 11 1.4350; specific gravity, 24/ 20 C.,acid acceptor value (pyridine hydrochloride method) 94.1 per cent; molarrefraction, 43.77, calculated, 43.60 found.

Calculated Analysis Found for Carbon, percent 53. 6 54. 4 Hydrogen,percent 9.0 1 9.07

EXAMPLE 2 glycol substituted for the methyl ether of propylene glycol.The dipropylene glycol monomethyl ether was 7 a mixture of isomersresulting from the reaction of two mols of propylene oxide with one molof methanol. There Was obtained 535 parts of the aipha-glycerylchlorhydrin ether of dipropylene glycol monomcthyl ether, representing ayield of 74 per cent of theory. It boiled at a temperature of '125-136C. at a pressure of two millimeters of mercury, abs.

The alpha-glyceryl chlorhydrin ether of dipropylene glycol monomethylether thus obtained (535 parts, 2.22 mols) was dehydrochlorinatcdaccording to the procedure employed in Example 1, using for this purpose88.8 parts (2.22 mols) of sodium hydroxide in the form of a 50 per centaqueous concentrate. There was obtained 408 parts of the glycidyl etherof the methyl ether of dipropylene glycol, which represented a yield of90 per cent of theory. The product was a colorless, limpid liquid thatwas miscible with water in all proportions. It was characterized by thefollowing properties: boiling temperature, 83 to 91 C. at a pressure of3 millimeters of mercury, abs.; specific gravity 24/20 C., 1.0010;refractive index, u 1,4313; and acceptor value (pyridine hydrochloridemethod) 94.9 per cent; molar refraction, 53.006 calculated; 52.81 found.

This application is in part a continuation of our applie cation filedJanuary 19, 1951, Serial No. 206,908.

We claim:

1. Water-miscible glycidyl ethers of the monomethyl ether of diglycolsin which the total number of carbon atoms in the molecule is from eightto ten with from two to three carbon atoms to each glycol radicalthereof.

2. Water-miscible glycidyl ethers which convert on polymerization towater'miscible polymers, said ethers being of the general formula 011.0011111200 (02mm) OOH;C\H/CH1 in which R and R are of the groupconsisting of hydrogen and methyl.

3. The methyl, glycidyl diether of diethylene glycol.

0 4, The methyl, glycidyl diether of dipropylene glycol.

References Cited in the file of this patent UNITED STATES PATENTS

1. WATER-MISCIBLE GLYCIDYL ETHER OF THE MONOMETHYL ETHER OF DIGLYCOLS INWHICH THE TOTAL NUMBER OF CARBON ATOMS IN THE MOLECULE IS FROM EIGHT TOTEN WITH FROM TWO TO THREE CARBON ATOMS TO EACH GLYCOL RADICAL THEREOF.